Improving Photocatalysis for the Reduction of CO_2 through non-Covalent Supramolecular Assembly
Abstract
We report the enhancement of photocatalytic performance by introduction of hydrogen-bonding interactions to a Re bipyridine catalyst and Ru photosensitizer system (ReDAC/RuDAC) by the addition of amide substituents, with carbon monoxide (CO) and carbonate/bicarbonate as products. This system demonstrates a more-than-3-fold increase in turnover number (TON_(CO) = 100 ± 4) and quantum yield (Φ_(CO) = 23.3 ± 0.8%) for CO formation compared to the control system using unsubstituted Ru photosensitizer (RuBPY) and ReDAC (TON_(CO) = 28 ± 4 and Φ_(CO) = 7 ± 1%) in acetonitrile (MeCN) with 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as sacrificial reductant. In dimethylformamide (DMF), a solvent that disrupts hydrogen bonds, the ReDAC/RuDAC system showed a decrease in catalytic performance while the control system exhibited an increase, indicating the role of hydrogen bonding in enhancing the photocatalysis for CO_2 reduction through supramolecular assembly. The similar properties of RuDAC and RuBPY demonstrated in lifetime measurements, spectroscopic analysis, and electrochemical and spectroelectrochemical studies revealed that the enhancement in photocatalysis is due not to differences in intrinsic properties of the catalyst or photosensitizer, but to hydrogen-bonding interactions between them.
Additional Information
© 2019 American Chemical Society. Received: July 3, 2019; Published: September 6, 2019. A grant from the U.S. Air Force Office of Scientific Research (AFOSR), Basic Research Initiative (BRI) (FA9550-12-1-0414), supported P.L.C., T.Z., and C.P.K. A grant from the U.S. Department of Energy, Office of Basic Energy Sciences (DE-SC0016450), supported S.C.K. and M.E.T. The authors declare no competing financial interest.Attached Files
Supplemental Material - ja9b07067_si_001.pdf
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Additional details
- Alternative title
- Improving Photocatalysis for the Reduction of CO2 through non-Covalent Supramolecular Assembly
- Eprint ID
- 98493
- DOI
- 10.1021/jacs.9b07067
- Resolver ID
- CaltechAUTHORS:20190906-134149533
- FA9550-12-1-0414
- Air Force Office of Scientific Research (AFOSR)
- DE-SC0016450
- Department of Energy (DOE)
- Created
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2019-09-06Created from EPrint's datestamp field
- Updated
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2021-11-16Created from EPrint's last_modified field